Composite reinforced micropore array glass material as well as preparation method and application thereof

Abstract

The invention relates to a composite reinforced micropore array glass material as well as a preparation method and application thereof. The method comprises the following steps: immersing a micropore array glass material into a molten salt solution to carry out ion exchange reaction; cooling the reacted microporous array glass material to room temperature, cleaning and drying, and depositing a repairing film layer inside and outside the pores of the microporous array glass material by an atomic layer deposition method; and carrying out annealing micro-crystallization treatment on the coated microporous array glass material to obtain the composite reinforced microporous array glass material. According to the invention, by adopting a composite strengthening process of first carrying out molten salt ion exchange chemical strengthening, then carrying out atomic layer deposition to repair a film layer, and finally carrying out high-temperature annealing microcrystallization, the prepared microporous array glass material has relatively high mechanical strength.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of porous structure glass strengthening, in particular to a composite strengthened microporous array glass material and a preparation method and application thereof. BACKGROUND

[0002] The microporous array glass material is a thin sheet glass-based material with millions of micron-level through-hole structures, has a large aspect ratio, a large duty ratio, a large specific surface area, high pore size accuracy, high temperature resistance, acid and alkali corrosion resistance and the like, is mainly used as a light beam particle beam collimator, an X-ray focusing lens, a cell filter separator, an electrolyte membrane support, a catalyst loading substrate and the like, and is widely applied in the fields of aerospace, particle detection, biological medicine, energy cells and the like. However, due to the thin sheet porous structure, the microporous array glass material has low mechanical strength and is prone to cracks when subjected to vibration and impact, resulting in a shortened service life and failing to meet the urgent needs of the user end for long service life.

[0003] However, the current glass strengthening technology is a technology for enhancing the mechanical strength of glass blocks and glass sheets, and there is no suitable strengthening technology for thin sheet microporous array glass materials. Compared with conventional glass blocks or sheets, the thin sheet microporous array glass material has millions of micron-level through-hole structures, has a large duty ratio, a large specific surface area, a large aspect ratio and thin pore walls, and the conventional glass block and glass sheet strengthening process technology cannot guarantee the uniformity and consistency of the strengthening layers inside and outside the through holes of the microporous array glass material, resulting in limited overall mechanical strength enhancement, difficult to overcome the service life problem, and failing to meet the urgent needs of the user end for long service life microporous array glass materials. Therefore, how to obtain a microporous array glass material with high mechanical strength has become a technical problem to be solved. SUMMARY

[0004] Therefore, the main purpose of the present application is to provide a composite strengthened microporous array glass material and a preparation method and application thereof, and the technical problem to be solved is to make the prepared microporous array glass material have high mechanical strength by adopting a composite strengthening process of “first molten salt ion exchange chemical strengthening, then atomic layer deposition repair film, and finally high temperature annealing microcrystallization”.

[0005] The purpose of the present application and the technical problem thereof are realized by adopting the following technical scheme. The present application provides a preparation method of a composite strengthened microporous array glass material, including the following steps:

[0006] 1) immersing the microporous array glass material in a molten salt solution for ion exchange reaction;

[0007] 2) cooling the microporous array glass material after the reaction of step 1) to room temperature, cleaning, drying, and depositing a repair film layer on the inside and outside of the microporous array glass material by atomic layer deposition;

[0008] 3) annealing and microcrystallizing the microporous array glass material after the film coating of step 2) to obtain the composite strengthened microporous array glass material.

[0009] Preferably, in the method for preparing the composite strengthened microporous array glass material, the molten salt solution in step 1) is a sodium salt and a potassium salt solution.

[0010] Preferably, in the method for preparing the composite strengthened microporous array glass material, the sodium salt in step 1) is selected from one of sodium nitrate, sodium nitrite and sodium bicarbonate, and has a purity of greater than or equal to 99.9%; the potassium salt is selected from one of potassium nitrate and potassium tartrate, and has a purity of greater than or equal to 99.9%.

[0011] Preferably, in the method for preparing the composite strengthened microporous array glass material, the ion exchange reaction time in step 1) is 10 min to 8 h.

[0012] Preferably, in the method for preparing the composite strengthened microporous array glass material, the ion exchange reaction temperature in step 1) is less than or equal to the viscous flow temperature Tf of the microporous array glass material.

[0013] Preferably, in the method for preparing the composite strengthened microporous array glass material, the material of the repair film layer in step 2) is selected from one of SiO2, Al2O3, TiO2 and ZrO2, and has a thickness of 50-300 nm.

[0014] Preferably, in the method for preparing the composite strengthened microporous array glass material, the annealing temperature in step 3) is less than or equal to the viscous flow temperature Tf of the microporous array glass material.

[0015] Preferably, in the method for preparing the composite strengthened microporous array glass material, the annealing time in step 3) is 10 min to 1 h.

[0016] The purposes and technical problems of the present application can also be further achieved by the following technical measures. The present application provides a composite strengthened microporous array glass material, which comprises a glass substrate, and a plurality of microporous units distributed on the glass substrate.

[0017] Preferably, in the composite strengthened microporous array glass material, the outer contour of the microporous array glass material is in the shape of a rectangle, a circle, a polygon or a ring.

[0018] Preferably, in the composite strengthened microporous array glass material, the cross section of the microporous array glass material is planar, stepped or curved.

[0019] Preferably, in the composite strengthened microporous array glass material, the distribution of the microporous units is selected from at least one of square arrangement, hexagonal close-packed arrangement, linear arrangement, divergent arrangement and ring arrangement.

[0020] Preferably, in the composite strengthened microporous array glass material, the longitudinal section of the microporous units is rectangular, trapezoidal, flat-top Gaussian or hourglass-shaped.

[0021] Preferably, in the composite strengthened microporous array glass material, the thickness of the microporous array glass material is 0.3-5mm, the end surface coverage ratio of the microporous units is 30%-90%, and the characteristic size of the microporous units is 4-500μm.

[0022] The purposes and technical problems of the present application can also be further achieved by the following technical measures. The present application provides a component using the composite strengthened microporous array glass material.

[0023] Preferably, in the component, the component is a light beam particle beam collimator, an X-ray focusing lens, a cell filtration separator, an electrolyte membrane support or a catalyst loading substrate.

[0024] By the above technical solutions, the composite strengthened microporous array glass material, its preparation method and application provided by the present application have at least the following advantages:

[0025] Compared with the conventional method of using a single method to inhibit the propagation probability of microcracks or reduce the number of surface microcrack defects, the composite strengthening technology used in the present application combines the reduction of the number of surface microcrack defects and the inhibition of the propagation probability of microcracks, effectively improves the mechanical strength of the microporous array glass material, solves the strengthening problem of the current microporous array glass material and other porous structure glass sheets, and meets the application requirements in related fields.

[0026] Compared with conventional thin film coating technology, the atomic layer deposition technology is used to prepare the repair film layer on the surface of the micropore array glass material in the application. The atomic layer deposition technology is the most suitable method for preparing the surface thin film of the porous structure glass sheet through multiple test verifications, can meet the uniform thin film preparation of the surface of the large length-diameter ratio and complex three-dimensional micropore structure, realizes the formation of the uniform thin film covering layer on the inner wall surface of the micropore array glass material, effectively fills and repairs the microcrack defects on the surface of the micropore array glass material, effectively improves the mechanical strength of the micropore array glass material and the like porous structure glass sheet, and meets the application requirements in related fields.

[0027] The application realizes the passivation of the microcrack defects on the inner and outer surfaces of the glass pores of the micropore array glass material substrate through high-temperature annealing microcrystallization, the strong combination of the glass substrate and the thin film layer, and the effective dispersion of the stress concentration of the film layer microcrystallization structure, reduces the crack propagation probability, and at the same time, increases the dislocation movement resistance of the film layer, thereby improving the mechanical strength of the micropore array glass material and the like porous structure glass sheet, and meeting the application requirements in related fields.

[0028] The above description is only a summary of the technical scheme of the application, in order to more clearly understand the technical means of the application, and the content of the description can be implemented as follows. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 The preparation process flow chart of the composite strengthened micropore array glass material of some embodiments of the application;

[0030] Figure 2 The schematic diagram of the top view of the outline profile of the composite strengthened micropore array glass material of some embodiments of the application (1-rectangular, 2-circular, 3-polygonal, 4-regular polygon, 5-ring-shaped);

[0031] Figure 3 The schematic diagram of the cross section of the outline profile of the composite strengthened micropore array glass material of some embodiments of the application (6-flat type, 7-step surface type, 8-curved surface type);

[0032] Figure 4 The schematic diagram of the top view of the micropore unit of the composite strengthened micropore array glass material of some embodiments of the application (9-rectangular, 10-circular, 11-triangular, 12-polygonal);

[0033] Figure 5 The schematic diagram of the arrangement and distribution of the micropore unit of the composite strengthened micropore array glass material of some embodiments of the application (13-quadrilateral arrangement, 14-hexagonal close-packed, 15-linear arrangement, 16-divergent arrangement, 17-ring-shaped arrangement);

[0034] Figure 6 Longitudinal cross-section of micro-holes of composite strengthened micro-holes array glass material (18-rectangular, 19-trapezoidal, 20-flat-top Gaussian, 21-hourglass) according to some embodiments of the present application;

[0035] Figure 7 Square array of micro-holes array of composite strengthened micro-holes array glass material (22-square holes) according to some embodiments of the present application;

[0036] Figure 8 Hexagonal close-packed array of micro-holes array of composite strengthened micro-holes array glass material (23-circular holes) according to some embodiments of the present application. DETAILED DESCRIPTION

[0037] To further illustrate the technical means and effects taken by the present application to achieve the intended purpose, the following describes the specific embodiments, structures, features, and effects of a composite strengthened micro-holes array glass material, a preparation method thereof, and applications thereof according to the present application. In the following description, different "an embodiment" or "embodiments" do not necessarily refer to the same embodiment. In addition, specific features, structures, or characteristics in one or more embodiments can be combined in any suitable form.

[0038] The following materials or reagents, unless otherwise specified, are commercially available.

[0039] As introduced in the background section, micro-holes array glass material is widely used in aerospace, particle detection, biomedicine, energy batteries, etc. due to its high pore size accuracy, large aspect ratio, high duty ratio, large specific surface area, high temperature resistance, acid and alkali corrosion resistance, etc. However, due to its thin sheet-like porous structure, the mechanical strength of the micro-holes array glass material is low, and cracks are easily generated when subjected to vibration and impact, resulting in a shorter service life and failing to meet the urgent needs of users for long service life. Therefore, in order to solve the above technical problems, the present application provides a composite strengthened micro-holes array glass material, a preparation method thereof, and applications thereof.

[0040] As shown in Figure 1 According to some embodiments of the present application, a preparation method of a composite strengthened micro-holes array glass material is provided, which comprises the following steps:

[0041] S1 ultrasonic cleaning of microporous array glass material in the purification workshop, drying for standby; drying is a conventional operation in the field of sample cleaning, and the commonly used drying methods include oven drying, hot air drying, volatile organic solvent assisted drying, vacuum drying and the like. According to different drying methods, the corresponding operation parameters are also different, and the drying temperature is usually within room temperature to 200 DEG C, and the drying time is within 5 min to 30 min. The drying time is to ensure that the moisture on the surface of the substrate is fully volatilized and evaporated. The purpose of heating is to promote the volatilization of moisture on the surface of the substrate. Similarly, using volatile organic solvents and vacuum assistance are also to promote the volatilization of moisture on the surface of the substrate, so that the cleaned microporous array glass material can be quickly dried, and the subsequent process operation is prepared.

[0042] S2, the microporous array glass material obtained in step S1 is loaded on the sample holder, and high-purity sodium potassium salt is used as the raw material of the molten salt, loaded into the crucible, covered with a cover, and placed in a low-temperature furnace; the sample holder is used to place the sample to make it stable and avoid obvious shaking, facilitating the immersion of the molten salt operation; and the sample holder is a conventional sample holder used for fixing and placing samples in the ion exchange field, and the material of the holder does not react with sodium potassium molten salt, which will not be described here;

[0043] S3 gradually heating the low-temperature furnace of step S2 to completely melt the sodium potassium salt into a molten salt solution;

[0044] S4 immersing the sample holder loaded with the microporous array glass material obtained in step S3 into the above molten salt solution for ion exchange reaction;

[0045] S5 taking out the microporous array glass material after the reaction of step S4, and slowly cooling to room temperature;

[0046] S6 cleaning the microporous array glass material obtained in step S5 with deionized water, and drying for standby;

[0047] S7 depositing a repair film layer on the microporous array glass material obtained in step S6 by using atomic layer deposition technology;

[0048] S8 loading the microporous array glass material after film plating in step S7 into a sample holder, and placing it in an annealing furnace for annealing and microcrystallization treatment; slowly heating the annealing furnace to the target temperature, and then slowly cooling to room temperature after holding, finally obtaining a composite strengthened microporous array glass material.

[0049] In some optional embodiments, the frequency range of the ultrasonic cleaning in step S1 can be set to 20 kHz to 1 MHz. The frequency is selected to ensure the effect of ultrasonic cleaning. The smaller the frequency, the greater the energy of the ultrasonic bubbles, which is suitable for structures with large pore diameters and thick pore walls. A smaller frequency, such as less than 20 kHz, can increase the probability of damage to the pore wall. The greater the frequency, the smaller the energy of the ultrasonic bubbles, which is suitable for structures with small pore diameters and thin pore walls. A greater frequency, such as greater than 1 MHz, can reduce the cleaning degree of the inner wall of the pore. Since the feature size of the micropores in the present application is in the range of 4-500 μm, the frequency range is suitable for a wide range of 20 kHz to 1 MHz. The frequency is preferably 80 kHz to 200 kHz. The power range can be selected to be 30 W to 300 W. The ultrasonic power mainly affects the number of ultrasonic bubbles. The smaller the power, the fewer the bubbles, and the lower the cleaning efficiency. Too low power, such as less than 30 W, can result in insufficient number of bubbles, which can cause some surfaces to be not cleaned, especially the inner surface of the micropore cannot be effectively cleaned. The greater the power, the more the bubbles, and the higher the cleaning efficiency. Too high power, such as greater than 300 W, can result in a sudden increase in the number of bubbles, and the impact force of the bubble burst is too large, which can increase the probability of physical damage to the inner and outer surfaces of the micropore array glass material, such as small scratches, pitting, and increased collision and friction between the substrate and the sample holder, which can cause damage to the surfaces in contact with each other, and increase the risk of damage to the micropore array glass material. Therefore, for the micropore array glass material, the power is preferably 100 W to 200 W. The ultrasonic time can be set to 1 min to 2 h. The ultrasonic cleaning time mainly affects whether the cleaning is sufficient. The longer the time, the more sufficient the action of the ultrasonic bubbles on the inner and outer surfaces of the micropore. However, too long time, such as more than 2 hours, can increase the physical damage caused by the back and forth vibration of the ultrasonic sample, and can also cause the impurities and pollutants stripped by cleaning to be re-adsorbed on the surface of the substrate if the time is not changed for a long time, especially when the concentration of impurities and pollutants is too high, which can cause the phenomenon of "the more you wash, the dirtier it gets". The shorter the time, the smaller the damage to the micropore array glass material sample caused by the ultrasonic bubbles. However, too short time, such as less than 1 minute, can not thoroughly clean the pollutants adhered to the surface, especially the cleaning dead angle inside the pore, and residual pollutants. Therefore, the ultrasonic time is preferably 5 min to 30 min.

[0050] In some optional embodiments, the crucible in step S2 is made of a high-temperature-resistant dense material, and common materials include quartz, corundum, quartz ceramic, AZS, platinum, and platinum alloy, and quartz is preferred. The crucible is used to hold the molten salt solution, and thus the material needs to be dense, resistant to several hundred degrees of high temperature, thermally stable, and not react with the molten salt solution. Common materials that meet the requirements include quartz, corundum, quartz ceramic, AZS, platinum, and platinum alloy. The cost of the noble metal platinum and platinum alloy is too high, and corundum, quartz ceramic, and AZS are prone to react with the molten salt over a long period of time. Quartz is the densest and has moderate cost and does not react with the molten salt, and thus is preferred as the crucible material.

[0051] In some optional embodiments, the sample holder in step S2 is made of a high-temperature-resistant dense material, and common materials include quartz, corundum, quartz ceramic, AZS, platinum, and platinum alloy, and quartz is preferred. The sample holder is used to hold the sample and make it stable, and thus the material needs to be dense, resistant to several hundred degrees of high temperature, thermally stable, and not react with the molten salt solution. Common materials that meet the requirements include quartz, corundum, quartz ceramic, AZS, platinum, and platinum alloy. The cost of the noble metal platinum and platinum alloy is too high, and corundum, quartz ceramic, and AZS are prone to react with the molten salt over a long period of time. Quartz is the densest and has moderate cost and does not react with the molten salt, and thus is preferred as the crucible material.

[0052] In some optional embodiments, the low-temperature furnace in step S2 is selected to have a working temperature in the range of room temperature to 600°C. The low-temperature furnace is used for the ion exchange reaction between the glass material and the molten salt solution, and the melting temperature of the sodium-potassium molten salt is 150°C to 350°C. The working temperature of the furnace is selected to be in the range of room temperature to 600°C to ensure that the ion exchange reaction can proceed smoothly. In general, the higher the working temperature of the furnace, the higher the cost, and the working temperature also needs to be lower than the viscous flow temperature Tf of the microporous array glass material. In summary, the working temperature of the furnace is selected to be in the range of room temperature to 600°C, and common furnaces include resistance heating furnaces, gas heating furnaces, and infrared heating furnaces. These three types of furnaces are commonly used low-temperature heating furnaces, are relatively economical and durable, and the resistance heating furnace is preferred because it is the most economical and suitable. The gas heating furnace needs to be provided with a gas cylinder or a gas pipeline, and there is a risk of gas leakage. The infrared heating furnace has high cost and its heating efficiency depends on the properties of the molten salt, and thus has relatively poor universality. The low-temperature furnace is used to provide external heat to the molten salt for the ion exchange reaction to fully melt the molten salt, and to complete the diffusion of sodium and potassium ions along the depth direction of the surface layer of the microporous glass material at a certain temperature. The low-temperature furnace needs to be economical, durable, and easy to operate.

[0053] In some optional embodiments, in step S2, the sodium salt is sodium nitrate, sodium nitrite or sodium bicarbonate, preferably sodium nitrate; and the potassium salt is potassium nitrate or potassium tartrate, preferably potassium nitrate, preferably with a purity of 99.9% or more. The melting point of sodium nitrate is 308°C, the melting point of sodium nitrite is 271°C, the melting point of sodium bicarbonate is 270°C, the melting point of potassium nitrate is 334°C, and the melting point of potassium tartrate is 155°C. As a raw material of fused salt, the sodium and potassium salt is required to have a melting point lower than the viscous flow temperature Tf of the microporous array glass material, and the higher the melting point, the higher the reaction temperature, and the less gas released, ensuring the safety and stability of the experiment. Therefore, the sodium salt is sodium nitrate, and the potassium salt is potassium nitrate.

[0054] In some optional embodiments, in step S4, the ion exchange reaction time is 10 min to 8 h, preferably 30 min to 2 h. The ion exchange layer is too thin when the ion exchange reaction time is less than 10 min, and the strengthening effect is not obvious; the ion exchange layer is too thick when the ion exchange reaction time is more than 8 h, the surface extrusion effect is reduced, the strengthening effect is significantly attenuated, and the strengthening effect is better. According to the actual experimental results, it is found that when the reaction time is 30 min to 2 h, the strengthening effect is better.

[0055] In some optional embodiments, in step S4, the ion exchange reaction temperature and the annealing temperature of the microporous array glass material are both not higher than the viscous flow temperature Tf of the glass. When the reaction temperature and the annealing temperature are higher than the viscous flow temperature Tf of the glass, the microporous array glass material is prone to softening deformation, resulting in the product shape specification failing to meet the use requirements. Therefore, in order to avoid this problem, the reaction temperature and the annealing temperature need to be controlled to be not higher than the viscous flow temperature Tf of the glass. For example, when the microporous array glass material Tf = 600°C, the ion exchange reaction temperature is not higher than 600°C, and the annealing temperature is not higher than 600°C.

[0056] In some optional embodiments, in step S7, the repair film layer coated on the surface is selected from a thin film material with strong bonding to the glass and a dense film layer, such as SiO2, Al2O3, TiO2 or ZrO2, preferably SiO2 and Al2O3. SiO2, Al2O3, TiO2 or ZrO2 film layers usually have strong bonding to the glass substrate and a dense film layer, while silicon dioxide and aluminum oxide are usually the main components of glass materials. The use of SiO2 and Al2O3 film layers can enhance the bonding to the glass substrate, so SiO2 or Al2O3 is preferred; generally, the film layer thickness is 50nm to 300nm, preferably 100nm to 200nm. According to actual experimental results, when the film thickness is less than 50nm, the film is too thin and the repair effect on surface microcrack defects is poor. When the film thickness is greater than 300nm, during the subsequent annealing microcrystallization process, due to the excessive thickness of the film, the micrograins grow significantly and the grain boundaries are obvious, which easily creates new stress concentration points and leads to strengthening attenuation. Therefore, the film thickness is selected to be 50nm to 300nm. According to experimental results, when the film thickness is between 100nm and 200nm, the actual strengthening effect is better, so the film thickness in this range is preferred.

[0057] Atomic layer deposition technology is used to deposit the surface repair film layer. Due to the characteristics of micropore array materials such as small micropore size, large aspect ratio, and thin pore wall, conventional physical vapor deposition coating methods (such as magnetron sputtering, electron beam evaporation, thermal evaporation, etc.) cannot effectively coat the film layer inside the micropores. Conventional chemical vapor deposition coating methods (such as chemical vapor deposition) cannot uniformly coat the film layer inside the micropores. Other methods such as brushing and spraying are prone to cause problems such as micropore blockage and uneven film layer on the inner wall of the pore. Therefore, after comparing various film preparation methods, it was found that currently only atomic layer deposition technology is suitable for the preparation of uniform film layers inside and outside the pores of micropore array materials.

[0058] In some optional embodiments, in step S8, the annealing sample holder is made of stainless steel, quartz, or ceramic, preferably stainless steel. The annealing sample holder needs to be resistant to high temperatures, have a dense surface, and not easily rubbed off. Commonly used materials include stainless steel, quartz, and ceramic. Quartz and ceramic are brittle materials and easily damaged by bumps, while stainless steel is not afraid of bumps, is safer, and is more durable. Therefore, stainless steel is preferably used.

[0059] In some optional embodiments, the annealing time in step S8 is 10 min to 1 h, and the annealing time is preferably 20 min to 40 min. When the annealing time is less than 10 min, the time is too short, the microcrystallization degree of the film layer is not high, and the strengthening effect is not ideal. When the annealing time is more than 1 h, the time is too long, the crystallization degree of the film layer is high, and when the film layer is thick, the grain growth is obvious, the grain boundary is obvious, and a new stress concentration point is easily generated, resulting in attenuation of the strengthening. Therefore, the annealing time is selected to be 10 min to 1 h. It is found through experimental results that when the annealing time is 20 min to 40 min, the microcrystallization degree of the film layer is moderate, and the actual strengthening effect is good.

[0060] According to some embodiments of the present application, a composite strengthened micropore array glass material is provided, which comprises a glass substrate, and a plurality of micropore units distributed on the glass substrate.

[0061] In some optional embodiments, the outer shape of the micropore array glass material is a rectangle 1 (including rectangular deformation cases such as a square and a rhombus), a circle 2 (including circular deformation cases such as an ellipse), a polygon 3 (including equilateral regular polygons such as a regular hexagon, and irregular polygons such as a trapezoid), or a ring 5 (a ring shape with a hollow center region such as a circular ring or a square ring), as shown in FIG. 1. Figure 2 The outer shape is determined according to user product requirements, and commonly used shapes include a rectangle (including rectangular deformation cases such as a square and a rhombus), a circle (including circular deformation cases such as an ellipse), a polygon (including equilateral regular polygons such as a regular hexagon, and irregular polygons such as a trapezoid), and a ring (a ring shape with a hollow center region such as a circular ring or a square ring).

[0062] In some optional embodiments, the cross-sectional side view of the outer shape of the micropore array glass material is a rectangle 6, a stepped surface 7, or a curved surface 8 (including spherical and aspherical surfaces), as shown in FIG. 2. The cross-sectional shape of the micropore array glass material is determined according to user product requirements. Figure 3

[0063] In some optional embodiments, the outer shape of the micropore unit of the micropore array glass material is a rectangle 9 (including rectangular deformation cases such as a square and a rhombus), a circle 10 (including circular deformation cases such as an ellipse), a triangle 11 (including equilateral regular triangles), or a polygon 12 (including equilateral regular polygons such as a regular hexagon, and irregular polygons such as a trapezoid), as shown in FIG. 3. The outer shape of the micropore unit is determined according to user product requirements. Figure 4

[0064] ​​In some alternative embodiments, the micropore unit arrangement of the micropore array glass material is arranged in a square arrangement 13, a hexagonal close-packed arrangement 14, a linear arrangement 15, a divergent arrangement 16, or a ring arrangement 17, as shown in FIG. 1. Figure 5 The arrangement of the micropore units can be determined according to the requirements of the user product.

[0065] In some alternative embodiments, the longitudinal cross section of the micropore unit is rectangular 18, trapezoidal 19, flat-topped Gaussian 20, or hourglass-shaped 21, as shown in FIG. 2. Figure 6

[0066] In some alternative embodiments, the thickness of the micropore array glass material is 0.3 mm to 5 mm, and the end surface area ratio of the micropore unit is 30% to 90%. The end surface area ratio of the micropore unit refers to the ratio of the total area of the micropore end surfaces in the micropore array to the total area of the end surfaces of the glass material. The greater the end surface area ratio, the more micropores there are, and the greater the utilization rate of the micropores. The smaller the end surface area ratio, the fewer micropores there are, and the smaller the utilization rate of the micropores. Generally, the end surface area ratio of the micropore unit tends to be as large as possible, but the thickness of the pore wall also needs to be considered. The micropore structure needs to meet the use strength, and therefore, the end surface area ratio of 90% is close to the limit of the micropore structure. Therefore, the end surface area ratio of the micropore unit is selected to be 30% to 90%. The characteristic dimension of the micropore unit is 4 μ m to 500 μ m, wherein the characteristic dimension of the micropore unit refers to the diameter of the largest inscribed circle of the cross section of the micropore or the length of the largest major axis of the cross section of the elliptical hole.

[0067] In the above technical solution, the present application innovatively adopts a composite strengthening process of "first molten salt ion exchange chemical strengthening, then atomic layer deposition of a repair film, and finally high-temperature annealing of microcrystallization", and by continuously optimizing and adjusting the process parameters such as the reaction temperature, reaction time, stirring rate of the molten salt, type and deposition temperature of the repair film, thickness of the film, and annealing temperature and annealing time, a composite strengthening technology suitable for thin sheet micropore array glass materials is finally formed. The thin sheet micropore array glass material prepared has the characteristics of high mechanical strength and can meet the use requirements of micropore array glass materials with long service life.

[0068] According to some embodiments of the present application, a light beam particle beam collimator is provided, which adopts the composite strengthened micropore array glass material described above. The micropores of the light beam collimator are generally circular holes with a diameter of 1-10 μm, and the micropores of the particle beam collimator are generally circular holes with a diameter generally greater than 200 μm. The longitudinal cross section of the micropore is required to be rectangular, and the end surface area ratio is generally greater than 50%. The mechanical strength is determined by the working environment, such as the mechanical strength requirement of the ground station light beam particle beam collimator, which is low, and the mechanical strength requirement of the vehicle-mounted, airborne or space light beam particle beam collimator, which is high.​

[0069] According to some embodiments of the present application, an X-ray focusing lens is provided, which employs the composite reinforced micro-holes array glass material described above. The X-ray focusing lens is usually square micro-holes array arranged in a square array, the micro-holes feature size is usually 10-300 μm, the micro-holes longitudinal section is required to be rectangular or square, and the duty cycle is usually greater than 50%. The mechanical strength is determined by the working environment, such as the X-ray focusing lens for medical equipment usually has no special requirement for mechanical strength, while the X-ray focusing lens for space application requires to withstand high frequency vibration impact.

[0070] According to some embodiments of the present application, a cell filtration separator is provided, which employs the composite reinforced micro-holes array glass material described above. The cell filtration separator is usually round holes or regular hexagonal holes arranged in a hexagonal close-packed or square array, the micro-holes longitudinal section is required to be rectangular or trapezoidal, and the micro-holes feature size is determined by the filtration target, such as the diameter of red blood cell is about 7-8 μm, the diameter of white blood cell is about 10-15 μm, and the diameter of tumor cell is about 15-30 μm. In order to ensure the mechanical strength of the structure, the duty cycle is usually not higher than 40%.

[0071] According to some embodiments of the present application, an electrolyte membrane support is provided, which employs the composite reinforced micro-holes array glass material described above. The electrolyte membrane support is usually round holes or regular hexagonal holes arranged in a hexagonal close-packed, the micro-holes longitudinal section is usually required to be rectangular or square, the micro-holes feature size is usually less than 10 μm, and the duty cycle is usually between 30% and 70%.

[0072] According to some embodiments of the present application, a catalyst loading substrate is provided, which employs the composite reinforced micro-holes array glass material described above. The catalyst loading substrate is usually round holes or regular hexagonal holes arranged in a hexagonal close-packed, the micro-holes longitudinal section is usually required to be trapezoidal or hourglass-shaped, and the micro-holes feature size is usually greater than 1 μm. In order to ensure the overall catalytic efficiency and take into account the mechanical strength of the structure, the duty cycle is usually between 30% and 70%.

[0073] The present application provides these embodiments in order to make the present application thorough and complete, and fully express the scope of the present application to those skilled in the art. It should be noted that: unless otherwise specifically stated, the relative arrangement of components and steps, the composition of materials, numerical expressions and values set forth in these embodiments should be interpreted as merely exemplary, and not as a limitation.

[0074] The present application will be further described in conjunction with specific embodiments below, but it should not be understood as a limitation on the scope of protection of the present application. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present application described above still belong to the scope of protection of the present application.

[0075] Unless otherwise specified, the materials and reagents mentioned below are commercially available products familiar to those skilled in the art. Unless otherwise specified, the methods described are all well-known methods in the art. Unless otherwise defined, technical or scientific terms used shall have the same meanings as those commonly understood by those skilled in the art.

[0076] Example 1

[0077] This embodiment provides a method for preparing a composite strengthened microporous array glass material, comprising the following steps:

[0078] S1 uses square hole microporous array glass material as the strengthening object (such as Figure 4 As shown), the matrix glass is alkali aluminosilicate glass (its composition by mass percentage is, SiO2: 40wt%; Pb2O3: 20wt%; Al2O3: 10wt%; (Li2O+Na2 O+K2O): 15wt%; SnO2: 1wt%; BaO: 3wt%; (CaO+MgO): 6wt%; ZnO: 3wt%; TiO2: 2wt%), Tf = 590℃, the material thickness is 1.5mm, and the square holes are arranged in a square pattern (as shown). Figure 7 As shown, it includes a plurality of square holes 22), a duty cycle of 65%, and a micropore longitudinal cross-section of a rectangle (such as Figure 6 ), the micropore characteristic size is 100 μm; in a clean workshop (humidity of 50%, temperature of 23°C, workshop cleanliness level ISO 6), first use ultrasonic cleaning to remove surface pollutants, wherein the ultrasonic frequency is 40 kHz, the power is 100 W, and the ultrasonic time is 10 minutes (first ultrasonic in deionized water for 5 minutes, then ultrasonic in anhydrous ethanol for 5 minutes), and then dry for use (using a volatile organic solvent-assisted drying method, that is, using isopropyl alcohol and ultrasonic for 2 minutes, and then placing it in a drying oven for auxiliary evaporation drying, the drying temperature is 180°C, and the drying time is 10 minutes);

[0079] S2: The microporous array glass material is placed on a quartz rack. Sodium nitrate and potassium nitrate with a purity of ≥99.9% are used as molten salt raw materials in a mass ratio of 1:1. The molten salts are placed in a quartz crucible, covered with a lid, and placed together in a low-temperature furnace.

[0080] S3 gradually heats the low-temperature furnace to 350°C at a heating rate of 2°C / min, so that the sodium nitrate and potassium nitrate salts are completely melted into a molten salt solution;

[0081] S4: immersing the quartz frame containing the microporous array glass material into the molten salt solution to perform an ion exchange reaction, wherein the stirring rate of the molten salt is 5 rpm and the reaction time is 2 h;

[0082] S5: The microporous array glass material after the above reaction is taken out and slowly cooled to room temperature in the furnace at a rate of 0.5°C / min;

[0083] S6: The microporous array glass material is immersed in deionized water and then ultrasonically cleaned. After cleaning, the microporous array glass material is dried for standby use. The immersion time is 5 min, the ultrasonic frequency is 80 kHz, the power is 100 W, and the ultrasonic time is 5 min.

[0084] S7: A silicon dioxide film is deposited on the surface of the microporous array glass material by atomic layer deposition technology. Liquid tetraethoxysilane (TEOS) is used as the silicon source, and a 50°C temperature-controlled heating belt (commercially available) is provided on the source bottle to ensure the silicon source vapor pressure. Deionized water is used as the oxygen source, and a 100°C temperature-controlled heating belt (commercially available) is provided on the source bottle to ensure the oxygen source vapor pressure. High-purity nitrogen (purity 99.999%) is used as the carrier gas and the purge gas. The deposition temperature is 200°C, the deposition rate is 0.1 nm / cycle, and the deposition film thickness is 100 nm.

[0085] S8: The microporous array glass material after the above film deposition is placed in a stainless steel frame and placed in an annealing furnace for annealing treatment. The annealing furnace is slowly heated to 500°C at a rate of 2°C / min, and then slowly cooled to room temperature at a rate of 0.5°C / min after holding for 30 min. Finally, a composite strengthened microporous array glass material is obtained.

[0086] The composite strengthened microporous array glass material obtained in this example is characterized by its mechanical strength, i.e., bending strength. The composite strengthened microporous array glass material obtained in this example has a bending strength of 75.57 MPa as tested by a bending strength tester.

[0087] Example 2

[0088] The difference between this example 2 and example 1 is that the reaction time in step S4 of this example is 1 h, and the other steps and parameters are the same as those of example 1.

[0089] The composite strengthened microporous array glass material obtained in this example is characterized by its mechanical strength, i.e., bending strength. The composite strengthened microporous array glass material obtained in this example has a bending strength of 65.83 MPa as tested by a bending strength tester.

[0090] Example 3

[0091] The difference between this example 3 and example 1 is that the reaction time in step S4 of this example is 2.5 h, and the other steps and parameters are the same as those of example 1.

[0092] The composite strengthened micropore array glass material obtained in this example is characterized by the bending strength. The bending strength of the composite strengthened micropore array glass material obtained in this example is 68.19 MPa, tested by a bending strength tester.

[0093] Example 4

[0094] The difference between this example 4 and example 1 is that the micropore feature size in step S1 of this example is 50 μm, and the rest of the steps and parameters are the same as those in example 1.

[0095] The composite strengthened micropore array glass material obtained in this example is characterized by the bending strength. The bending strength of the composite strengthened micropore array glass material obtained in this example is 70.20 MPa, tested by a bending strength tester.

[0096] Example 5

[0097] The example provides a preparation method of a composite strengthened micropore array glass material, comprising the following steps:

[0098] S1, using a circular hole micropore array glass material as a strengthening object (as shown in Figure 4 The base glass is an alkali silicate glass (its composition is, in terms of mass percentage, SiO2: 45 wt%; Pb2O3: 25 wt%; Al2O3: 3 wt%; (Li2O + Na2O + K2O): 15 wt%; SnO2: 1 wt%; BaO: 3 wt%; (CaO + MgO): 5 wt%; ZnO: 2 wt%; TiO2: 1 wt%) Tf = 583℃, the material thickness is 1.0 mm, the duty cycle is 60%, and the circular hole hexagonal close packing (as shown in Figure 8 The micropore longitudinal section is trapezoidal (as shown in Figure 6 The small opening end micropore feature size is 20 μm; in a purification workshop (humidity 40%, temperature 28℃, workshop cleanliness ISO 5 level), first use ultrasonic cleaning to remove the surface contaminants, wherein the ultrasonic frequency is 80 kHz, the power is 100 W, and the ultrasonic time is 10 min (first deionized water ultrasonic 5 min, then anhydrous ethanol ultrasonic 5 min), and then dry for standby (use volatile organic solvent assisted drying method, use anhydrous ethanol ultrasonic 2 min, take out and place in a drying oven for auxiliary volatile drying, drying temperature is 180℃, drying time is 30 min);

[0099] S2, load the above micropore array glass material into a quartz frame, at the same time use sodium nitrate and potassium nitrate salt with purity ≥99.9% as the raw material of the molten salt, the mass ratio of the two is 1:1, load into a quartz crucible and cover the lid, and put them into a low temperature furnace together;

[0100] S3, gradually increasing the temperature of the above low-temperature furnace to 400℃ at a rate of 5℃ / min, so that the sodium nitrate and potassium nitrate salt completely melts into a molten salt solution;

[0101] S4, immersing the above quartz frame containing the microporous array glass material into the above molten salt solution for ion exchange reaction, the stirring rate of the molten salt is 5rpm, and the reaction time is 1h;

[0102] S5, taking out the above reacted microporous array glass material, and slowly cooling it to room temperature in the furnace at a rate of 0.5℃ / min;

[0103] S6, immersing the above microporous array glass material in deionized water first, and then ultrasonic cleaning, after cleaning, drying for standby, wherein the immersion time is 5min, the ultrasonic frequency is 80kHz, the power is 100W, and the ultrasonic time is 5min;

[0104] S7, depositing an aluminum oxide film on the surface of the above microporous array glass material by atomic layer deposition technology, wherein liquid trimethylaluminum (TMA) is used as the aluminum source, the source bottle is provided with a 25℃ temperature control heating belt (purchased on the market) to ensure the aluminum source vapor pressure; deionized water is used as the oxygen source, the source bottle is provided with a 100℃ temperature control heating belt (purchased on the market) to ensure the oxygen source vapor pressure; high-purity nitrogen (99.999%) is used as the carrier gas and the purge gas; the deposition temperature is 180℃, the deposition rate is 0.1nm / cycle, and the deposition film thickness is 150nm;

[0105] S8, placing the above coated microporous array glass material into a stainless steel frame and placing it into an annealing furnace for annealing treatment;

[0106] S9, slowly increasing the temperature of the annealing furnace to 500℃, keeping it for 40min, and then slowly cooling it to room temperature, finally obtaining a composite strengthened microporous array glass material, wherein the temperature increasing rate is 2℃ / min, and the temperature decreasing rate is 0.5℃ / min.

[0107] The composite strengthened microporous array glass material obtained in this example is characterized by bending strength. The bending strength of the composite strengthened microporous array glass material obtained in this example is 67.19MPa, tested by a bending strength tester.

[0108] Example 6

[0109] The difference between this embodiment 6 and embodiment 5 is that the thickness of the deposited film layer in step S7 of this embodiment is 50 nm, and the rest of the steps and parameters are the same as those in embodiment 5. The composite strengthened micropore array glass material obtained in this embodiment is characterized by its mechanical strength using the bending strength. The bending strength of the composite strengthened micropore array glass material obtained in this embodiment is 55.05 MPa, as tested by the bending strength tester.

[0110] Embodiment 7

[0111] The difference between this embodiment 7 and embodiment 5 is that the thickness of the deposited film layer in step S7 of this embodiment is 300 nm, and the rest of the steps and parameters are the same as those in embodiment 5. The composite strengthened micropore array glass material obtained in this embodiment is characterized by its mechanical strength using the bending strength. The bending strength of the composite strengthened micropore array glass material obtained in this embodiment is 62.67 MPa, as tested by the bending strength tester.

[0112] Embodiment 8

[0113] The embodiment provides a preparation method of a composite strengthened micropore array glass material, which comprises the following steps:

[0114] S1, using a regular hexagon hole micropore array glass material as a strengthening object (as shown in Figure 4 The base glass of the regular hexagon hole micropore array glass material is an alkali silicate glass (its composition is, in terms of mass percentage, SiO2: 50 wt%; Pb2O3: 20 wt%; Al2O3: 5 wt%; (Li2O+Na2O+K2O): 15 wt%; SnO2: 0 wt%; BaO: 3 wt%; (CaO+MgO): 5 wt%; ZnO: 1 wt%; TiO2: 1 wt%) Tf = 605 ℃, the material thickness is 0.5 mm, the regular hexagon hole is hexagonal close-packed (as shown in Figure 5 The base glass of the regular hexagon hole micropore array glass material is an alkali silicate glass (its composition is, in terms of mass percentage, SiO2: 50 wt%; Pb2O3: 20 wt%; Al2O3: 5 wt%; (Li2O+Na2O+K2O): 15 wt%; SnO2: 0 wt%; BaO: 3 wt%; (CaO+MgO): 5 wt%; ZnO: 1 wt%; TiO2: 1 wt%) Tf = 605 ℃, the material thickness is 0.5 mm, the regular hexagon hole is hexagonal close-packed (as shown in

[0115] S2, loading the above micropore array glass material on a quartz frame, at the same time using pure sodium nitrate and potassium nitrate salt with purity ≥ 99.9% as the raw material of the molten salt, the mass ratio of the two is 1:1, loading into a quartz crucible and covering the lid, and then putting them into a low-temperature furnace together;

[0116] S3, gradually increasing the temperature of the above low-temperature furnace to 500°C at a rate of 10°C / min, so that the sodium nitrate and potassium nitrate salt completely melts into a molten salt solution;

[0117] S4, immersing the above quartz frame containing the microporous array glass material into the above molten salt solution for ion exchange reaction, the stirring rate of the molten salt is 5 rpm, and the reaction time is 30 min;

[0118] S5, taking out the above microporous array glass material after reaction, and slowly cooling it to room temperature in the furnace, wherein the cooling rate is 0.5°C / min;

[0119] S6, immersing the above microporous array glass material in deionized water, then ultrasonic cleaning, and drying after cleaning for standby, wherein the immersion time is 5 min, the ultrasonic frequency is 80 kHz, the power is 100 W, and the ultrasonic time is 5 min;

[0120] S7, using atomic layer deposition technology to deposit a silicon dioxide film on the surface of the above microporous array glass material, wherein liquid tetraethoxysilane (TEOS) is used as the silicon source, the source bottle is provided with a 50°C temperature control heating belt (commercially available) to ensure the silicon source vapor pressure; deionized water is used as the oxygen source, the source bottle is provided with a 100°C temperature control heating belt (commercially available) to ensure the oxygen source vapor pressure; high-purity nitrogen (99.999%) is used as the carrier gas and the purge gas; the deposition temperature is 200°C, the deposition rate is 0.1 nm / cycle, and the deposition film thickness is 200 nm;

[0121] S8, loading the above coated microporous array glass material into a stainless steel frame and placing it in an annealing furnace for annealing treatment;

[0122] S9, slowly increasing the temperature of the annealing furnace to 550°C, keeping it for 60 min, and then slowly cooling it to room temperature, finally obtaining a composite strengthened microporous array glass material, wherein the temperature increasing rate is 2°C / min, and the temperature decreasing rate is 0.5°C / min.

[0123] The composite strengthened microporous array glass material obtained in this example is characterized by bending strength. The bending strength of the composite strengthened microporous array glass material obtained in this example is 62.29 MPa, tested by a bending strength tester.

[0124] Comparative Example 1

[0125] The comparative example is a square hole micropore array glass material, which has the same base glass as the strengthened object of Example 1, i.e., an alkali-silicate-aluminate glass (with a composition by mass percent of SiO2: 40 wt%; Pb2O3: 20 wt%; Al2O3: 10 wt%; (Li2O + Na2O + K2O): 15 wt%; SnO2: 1 wt%; BaO: 3 wt%; (CaO + MgO): 6 wt%; ZnO: 3 wt%; TiO2: 2 wt%) and Tf = 583°C, and a material thickness of 1.5 mm, square hole hexagonal close packing (as shown in FIG. 1), including a plurality of square holes 22, a duty cycle of 65%, a micropore longitudinal cross section of a rectangle (as shown in FIG. 2), and a micropore characteristic dimension of 100 μm. The square hole micropore array glass material of the comparative example was tested by a bending strength tester, and the bending strength of the square hole micropore array glass material was 29.52 MPa. Figure 7 Figure 6 The comparative example is a square hole micropore array glass material, which has the same base glass as the strengthened object of Example 1, i.e., an alkali-silicate-aluminate glass (with a composition by mass percent of SiO2: 40 wt%; Pb2O3: 20 wt%; Al2O3: 10 wt%; (Li2O + Na2O + K2O): 15 wt%; SnO2: 1 wt%; BaO: 3 wt%; (CaO + MgO): 6 wt%; ZnO: 3 wt%; TiO2: 2 wt%) and Tf = 583°C, and a material thickness of 1.5 mm, square hole hexagonal close packing (as shown in FIG. 1), including a plurality of square holes 22, a duty cycle of 65%, a micropore longitudinal cross section of a rectangle (as shown in FIG. 2), and a micropore characteristic dimension of 100 μm. The square hole micropore array glass material of the comparative example was tested by a bending strength tester, and the bending strength of the square hole micropore array glass material was 29.52 MPa.

[0126] Comparative Example 2

[0127] The comparative example is a square hole micropore array glass material, which has the same base glass as the strengthened object of Example 1, i.e., an alkali-silicate-aluminate glass (with a composition by mass percent of SiO2: 40 wt%; Pb2O3: 20 wt%; Al2O3: 10 wt%; (Li2O + Na2O + K2O): 15 wt%; SnO2: 1 wt%; BaO: 3 wt%; (CaO + MgO): 6 wt%; ZnO: 3 wt%; TiO2: 2 wt%) and Tf = 583°C, and a material thickness of 1.5 mm, square hole hexagonal close packing (as shown in FIG. 1), including a plurality of square holes 22, a duty cycle of 65%, a micropore longitudinal cross section of a rectangle (as shown in FIG. 2), and a micropore characteristic dimension of 100 μm. The square hole micropore array glass material of the comparative example was tested by a bending strength tester, and the bending strength of the square hole micropore array glass material was 29.52 MPa. Figure 8 Figure 6 The comparative example is a square hole micropore array glass material, which has the same base glass as the strengthened object of Example 1, i.e., an alkali-silicate-aluminate glass (with a composition by mass percent of SiO2: 40 wt%; Pb2O3: 20 wt%; Al2O3: 10 wt%; (Li2O + Na2O + K2O): 15 wt%; SnO2: 1 wt%; BaO: 3 wt%; (CaO + MgO): 6 wt%; ZnO: 3 wt%; TiO2: 2 wt%) and Tf = 583°C, and a material thickness of 1.5 mm, square hole hexagonal close packing (as shown in FIG. 1), including a plurality of square holes 22, a duty cycle of 65%, a micropore longitudinal cross section of a rectangle (as shown in FIG. 2), and a micropore characteristic dimension of 100 μm. The square hole micropore array glass material of the comparative example was tested by a bending strength tester, and the bending strength of the square hole micropore array glass material was 29.52 MPa.

[0128] Comparative Example 3

[0129] The comparative example is a square hole micropore array glass material, which has the same base glass as the strengthened object of Example 1, i.e., an alkali-silicate-aluminate glass (with a composition by mass percent of SiO2: 40 wt%; Pb2O3: 20 wt%; Al2O3: 10 wt%; (Li2O + Na2O + K2O): 15 wt%; SnO2: 1 wt%; BaO: 3 wt%; (CaO + MgO): 6 wt%; ZnO: 3 wt%; TiO2: 2 wt%) and Tf = 583°C, and a material thickness of 1.5 mm, square hole hexagonal close packing (as shown in FIG. 1), including a plurality of square holes 22, a duty cycle of 65%, a micropore longitudinal cross section of a rectangle (as shown in FIG. 2), and a micropore characteristic dimension of 100 μm. The square hole micropore array glass material of the comparative example was tested by a bending strength tester, and the bending strength of the square hole micropore array glass material was 29.52 MPa. Figure 5 ​​As shown in FIG, the duty cycle is 70%, the micropore longitudinal cross section is rectangular, and the micropore characteristic size is 50 μm. The bending strength tester test shows that the bending strength of the square hole micropore array glass material of this comparative example is 28.97 MPa.

[0130] Comparative Example 4

[0131] This comparative example is a square hole microporous array glass material, which is the same as the strengthening object of Example 4. Its base glass is alkali aluminosilicate glass (its composition by mass percentage is SiO2: 40wt%; Pb2O3: 20wt%; Al2O3: 10wt%; (Li2O+Na2O+K2O): 15wt%; SnO2: 1wt%; BaO: 3wt%; (CaO+MgO): 6wt%; ZnO: 3wt%; TiO2: 2wt%), Tf = 583°C, the material thickness is 1.5mm, and the square holes are arranged in a square pattern (such as Figure 7 As shown, it includes a plurality of square holes 22), a duty cycle of 65%, and a micropore longitudinal cross-section of a rectangle (such as Figure 6 The micropore characteristic size is 50 μm. The bending strength tester test shows that the bending strength of the square hole micropore array glass material of this comparative example is 28.89 MPa.

[0132] Comparative Example 5

[0133] This comparative example differs from Example 1 in that the reaction time in step S4 is 9 hours, and the remaining steps and parameters are the same as in Example 1. The mechanical strength of the composite-strengthened microporous array glass material obtained in this comparative example was characterized by flexural strength. Testing using a flexural strength testing machine revealed a flexural strength of 34.24 MPa.

[0134] Comparative Example 6

[0135] This comparative example differs from Example 5 in that the film thickness in step S7 is 400 nm, and the remaining steps and parameters are the same as in Example 5. The mechanical strength of the composite-strengthened microporous array glass material obtained in this comparative example was characterized by flexural strength. Testing using a flexural strength testing machine revealed a flexural strength of 28.51 MPa.

[0136] Comparative Example 7

[0137] The difference between the present comparative example and Example 5 is that the annealing furnace in step S9 of the present comparative example is slowly heated to 650℃, and the rest of the steps and parameters are the same as those in Example 5. The composite strengthened micropore array glass material obtained in the present comparative example is obviously deformed, and the mechanical strength thereof is characterized by the bending strength. The bending strength of the composite strengthened micropore array glass material obtained in the present comparative example is 11.29 MPa, as tested by a bending strength tester.

[0138] As can be seen by comparing Example 1, Example 2, Example 3 and Comparative Example 1, the bending strength of the composite strengthened micropore array glass material obtained in Example 1 is increased by 156% compared with that of Comparative Example 1, and the mechanical strength is significantly enhanced; the bending strength of the composite strengthened micropore array glass material obtained in Example 2 is increased by 123% compared with that of Comparative Example 1, and the mechanical strength is significantly enhanced, but is slightly lower than the enhancement level of Example 1; the bending strength of the composite strengthened micropore array glass material obtained in Example 3 is increased by 131% compared with that of Comparative Example 1, and the mechanical strength is significantly enhanced, but is slightly lower than the enhancement level of Example 1. It is shown that for the same specification of micropore array glass material, the composite strengthening process and method of the present application have a significant mechanical enhancement effect, and there is also an optimal reaction time.

[0139] As can be seen by comparing Example 1, Example 2 and Example 3, for the same specification of micropore array glass material, there is an optimal reaction time in the ion exchange chemical strengthening. If the optimal reaction time is lower, the ion diffusion layer is thinner, resulting in a weaker surface layer extrusion effect and a smaller bending strength; if the optimal reaction time is higher, the ion diffusion layer is thicker, resulting in a relaxation of the surface layer extrusion effect, which also causes the bending strength to decrease.

[0140] As can be seen by comparing Example 4 and Comparative Example 4, the bending strength of the composite strengthened micropore array glass material obtained in Example 1 is increased by 143% compared with that of Comparative Example 1, and the mechanical strength is significantly enhanced;

[0141] As can be seen by comparing Example 2 and Example 4, for the same specification of micropore array glass material, the smaller the pore size feature size, the thinner the pore wall, and the thinner the ion diffusion layer required to form the surface layer ion extrusion effect. Therefore, under the same reaction temperature, the ion exchange reaction can achieve a higher strengthening effect in a shorter time.

[0142] As compared with Comparative Example 5, Example 6, Example 7 and Comparative Example 2, the bending strength of the composite strengthened microporous array glass material obtained in Example 5 is increased by 138% as compared with Comparative Example 2, and the mechanical strength is significantly enhanced; the bending strength of the composite strengthened microporous array glass material obtained in Example 6 is increased by 95% as compared with Comparative Example 2, and the mechanical strength is significantly enhanced, but is lower than the enhancement level of Example 5; the bending strength of the composite strengthened microporous array glass material obtained in Example 7 is increased by 122% as compared with Comparative Example 2, and the mechanical strength is significantly enhanced, but is slightly lower than the enhancement level of Example 5; it is shown that, for the same specification of microporous array glass material, the composite strengthening process and method of the present application has a significant mechanical enhancement effect, and there is an optimal thickness of the repair film layer.

[0143] As compared with Comparative Example 5, Example 6 and Example 7, for the same specification of microporous array glass material, in the atomic layer deposition repair film layer, the thicker the film layer, the better the repair effect on the surface microcrack defects, but there is an optimal thickness value. When the thickness of the film layer is less than the optimal value, the film layer is thin, and the repair and filling of the microcrack defects are insufficient; when the thickness of the film layer is greater than the optimal value, the film layer is thick, and completely covers and fills the microcrack defects, but increases the probability of grain growth in the subsequent microcrystallization treatment, the grain boundary is more obvious, and the stress dispersion effect is weakened, resulting in a decrease in bending strength.

[0144] As compared with Comparative Example 8 and Comparative Example 3, the bending strength of the composite strengthened microporous array glass material obtained in Example 8 is increased by 115% as compared with Comparative Example 3, and the mechanical strength is significantly enhanced, which shows that, for the same specification of microporous array glass material, the composite strengthening process and method of the present application has a significant mechanical enhancement effect.

[0145] As compared with Comparative Example 5 and Comparative Example 2, the bending strength of the composite strengthened microporous array glass material obtained in Example 5 is increased by 138% as compared with Comparative Example 2, and the mechanical strength is significantly enhanced, but is slightly lower than the enhancement level of Example 1, which shows that, for different specifications of microporous array glass material, the optimal composite strengthening process parameters may be different, and the optimal composite strengthening effect may also be different.

[0146] As compared with Comparative Example 8 and Comparative Example 3, the bending strength of the composite strengthened microporous array glass material obtained in Example 8 is increased by 115% as compared with Comparative Example 3, and the mechanical strength is significantly enhanced, but is slightly lower than the enhancement level of Example 1, which shows that, for different specifications of microporous array glass material, the optimal composite strengthening process parameters may be different, and the optimal composite strengthening effect may also be different.

[0147] It can be seen from comparative example 1, example 3 and comparative example 5 that for the same specification of microporous array glass material, there is an optimal reaction time in ion exchange chemical strengthening. When the ion exchange reaction time is higher than the optimal value, the ion diffusion layer is thicker, resulting in relaxation of the surface layer extrusion effect, causing the bending strength to decrease, and especially when the ion exchange reaction time is too long, the ion diffusion layer is too thick, the surface layer extrusion effect is obviously relaxed, and the bending strength is not obviously enhanced.

[0148] It can be seen from comparative example 5, example 7 and comparative example 6 that for the same specification of microporous array glass material, in the atomic layer deposition repair film layer, the thicker the film layer, the better the repair effect on the surface microcrack defect, but there is an optimal thickness. When the film layer thickness is greater than the optimal value, the film layer is thicker, increasing the probability of grain growth in subsequent crystallization treatment, the grain boundary is more obvious, weakening the stress dispersion effect, resulting in a decrease in bending strength, and especially when the film layer thickness is too large, the grain growth is obvious in the crystallization treatment, the grain boundary is obvious, and new crack-like stress concentration distribution is generated at the grain boundary, resulting in a serious weakening of the bending strength enhancement effect.

[0149] It can be seen from comparative example 5 and comparative example 7 that for the same specification of microporous array glass material, when the annealing temperature is higher than the viscous flow temperature Tf, the microporous array glass material softens and deforms, on the one hand, the deformation will change the product size, which cannot meet the use requirements; on the other hand, the glass structure is relaxed after softening, and the bending strength is not enhanced, but is obviously reduced, which cannot meet the use requirements.

[0150] In the above examples, the description of each example has its own emphasis, and the parts not described in detail in a certain example can be referred to the related description of other examples.

[0151] The numerical range described in the present application includes all numerical values in the range, and includes a range value composed of any two numerical values in the range. Different numerical values of the same index appearing in all examples of the present application can be combined to form a range value.

[0152] The technical features in the claims and / or description of the present application can be combined, and the combination manner is not limited to the combination obtained by reference relationship in the claims. The technical solutions obtained by combining the technical features in the claims and / or description are also within the protection scope of the present application.

[0153] The above is only a preferred embodiment of the present application, and does not limit the present application in any form. Any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present application are still within the scope of the technical solutions of the present application.

Claims

1. A method for preparing a composite strengthened microporous array glass material, characterized in that: The following steps are involved: 1) Immersing the microporous array glass material in a molten salt solution to perform an ion exchange reaction; 2) cooling the microporous array glass material after the reaction in step 1) to room temperature, cleaning it, drying it, and depositing a repair film layer inside and outside the pores of the microporous array glass material by atomic layer deposition; 3) performing annealing and microcrystallization treatment on the microporous array glass material after the coating in step 2) to obtain the composite strengthened microporous array glass material.

2. The method for preparing the composite strengthened microporous array glass material according to claim 1, wherein: In step 1), the molten salt solution is a sodium salt or potassium salt solution.

3. The method for preparing the composite strengthened microporous array glass material according to claim 2, wherein: In step 1), the sodium salt is selected from one of sodium nitrate, sodium nitrite and sodium bicarbonate, and its purity is greater than or equal to 99.9%; the potassium salt is selected from one of potassium nitrate and potassium tartrate, and its purity is greater than or equal to 99.9%; the time of the ion exchange reaction is 10 minutes to 8 hours; and the temperature of the ion exchange reaction is less than or equal to the viscous flow temperature Tf of the microporous array glass material.

4. The method for preparing the composite strengthened microporous array glass material according to claim 1, wherein: In step 2), the material of the repair film layer is selected from one of SiO2, Al2O3, TiO2 and ZrO2, and its thickness is 50-300nm.

5. The method for preparing the composite strengthened microporous array glass material according to claim 1, wherein: In step 3), the annealing temperature is less than or equal to the viscous flow temperature Tf of the microporous array glass material; and the annealing time is 10 min-1 h.

6. A composite strengthened microporous array glass material, characterized in that: The composite strengthened microporous array glass material comprises a glass substrate on which a plurality of microporous units are distributed.

7. The composite strengthened microporous array glass material according to claim 6, wherein: The outer contour of the microporous array glass material is rectangular, circular, polygonal or annular when viewed from above; the cross-section of the outer contour of the microporous array glass material is flat, stepped or curved; the distribution of the majority of the microporous units is selected from at least one of a tetragonal arrangement, a hexagonal close-packed arrangement, a linear arrangement, a divergent arrangement and a ring arrangement; the longitudinal cross-section of the majority of the microporous units is rectangular, trapezoidal, a flat-top Gaussian shape or an hourglass shape.

8. The composite strengthened microporous array glass material according to claim 6, wherein: The thickness of the microporous array glass material is 0.3-5 mm, the end face duty ratio of the microporous unit is 30%-90%, and the characteristic size of the microporous unit is 4-500 mm. μ m.

9. A component, characterized in that It adopts the composite reinforced microporous array glass material described in any one of claims 6 to 8.

10. The component according to claim 9, characterized in that The components are a light beam particle beam collimator, an X-ray focusing lens, a cell filter separator, an electrolyte membrane support or a catalyst loading substrate.

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